Process of producing titanium compounds



1 I "UNITED: STATES P ENT OFFICE.

1 mm FARUP, or cHRIs'rIAiuA, NORWAY, ASSIGNOR 'ro TITAN co. A/S'. or NORWAY, or cnms'rnmm, NORWAY.

PROCESS OF PRODUCING TITANIUM COMPOUNDS To all whom it may concern Be it known that I, PEDER FARU'P, a subject of Norway, and a resident of Christiania,,Kingdom of Norway, have invented certain new and useful Improvements n Processes of- -Produjcing Titanium Com pounds, of which the following is a specification.

This invention relates to the manufacture oftitanium compounds, which are suitable for the production of pigments and for other Y purposes.

- The object ofthe invention is a method whereby such compounds can be produced from titaniferous iron ores with great economy, the method giving as a by-product nitrogen compounds suitable foruse as feruse materials which occur in nature, espequantity. .50

' cially ilmenite or similar titaniferous iron ores, as these are the titanium mater als .1 n'ost'readily available.

Broadly speaking the invention is carried out by heating such a titaniferous material containing iron together with a reducing agent in an atniosphere of nitrogen until a reaction takes place whereby a titanium-nitrogen compound, for example 'TiN, is formed-,and the iron present is reduced to the metallic state. If the reducing agent employed is carbon, there will be formed in f addition to titanium nitrid, also titanium 35 cyanonitrids. The iron is then removed from the titanium nitrogen compound either means of an acid which will dissolve the iron but not the titanium compounds. I have found .that in this way the principal part of .the iron compounds may be easily acid will easily react with the, above mentioned titanium nitrogen compounds even when emplo ed in a comparatively small he decomposition-is quickly started by th'e application" of .initial heat; but as the reaction is exothermic, no further heating is necessary after the reaction is once started; The-reaction will proceed with considerable speed and violence until a com- Specification of Letters Patent. Patented J 15 1920;

' No Drawing. Application filed February 2' 1918 Serial No. 219,407. 'Renewed April 4, 1919.- Serial No.

ing product forms a solid mass if the right 1 amount of sulfuric acid has been-employed.

I have found that this solid 'mass contains practically all the nitrogen of the titanium nitrogen compound in the form of am-- monium sulfate and'also titanium sulfate and small amounts of iron in the form of ferrous sulfate. These sulfates are soluble in water and on lixiviation a solution containing all these sulfates. will result. From this solution the titanium. may be precipitated in well known manner. As the iron in the solution is present in the divalent state .and the titanium to a great extent in the trivalent state it is possible to effect a practically complete separation of titanium compounds from iron compounds by precipitation by means of heating when'care is taken that suflicient trivalent titanium is presentto prevent the oxidation of divalent iron to trivalent iron.

In this connection reference may vbe had to Norwegian Patent No. 28,088,.which is embodied in U. '8. application-Sr. No. 196,316, filed October 12, 1917 The resulting precipitate, consisting principally of titanium hydrates and containing an undesired acid substance and traces only offiiron, is well adapted to further treatments whereby the said acid sub stance is eliminated andwhereby the product. resulting therefrom is by calcination converted wholly' or partly into crystalline titanium dioxid which possesses excellent qualitiesas a pigment. by. .meansof magnetic separation or by The solution from whichthe titanium 113 dratesv were precipitated" may be further-.'

treated to recover the ammoniumsulfate,

iron sulfate and free sulfuric acid remaining in the-,solution. i By utilizing the property of titaniumktoj combine with gaseous nitrogen in .consider-v able quantities, I. have fou a m thod o producing titanium" compounds which is ap'? plicable not only to the comparatively expeni I i sive pure titanium compounds but also to the ion 1 "25 process I proceed as follows: Ilmenite contitaniferous iron ores. At the same time that'nitrogn is fixed by-the titaniumof said ores the iron also contained therein is changed to a condition which facilitates its separation from. the titanium compounds. Further I have found that by this reduction process the titanium compounds present as pigment, and on the other hand ammo- 5 with nitrogen during I the ilmenite is practicallycomplet'ely "dc-- composed. This point can be determined by examining a sample from the furnace. The

14. material is. then crushed. to the fineness ofwhich serve to fix gaseous nitrogen are transformed to a condition in which they are process may lvary according to'the raw material used and the final products desired.

In the following specific illustration I will makeuse of ilmenite as araw material and carry out my process so as-to obtain on one handa titanium compound sultable foruse nium sulfate suitable for use as a fertilizer. The iron present in the ilmenite is transformed to ferrous sulfate. To carry out my tafiningapproximately TiO and 40% Fe. is finely pulverized and mixed with p'ul-.

verized carbon in a suflicient' amount to reduce the 1ron oxlds present to metalllc 1ron and also the-titanium oxid to titanium.- I

generally use an excess'of carbon as losses -may occur during the heating process and alsotitanium-cyanonitrid may be formed.

The mixture is brought into a. furnace, preferably an electric furnace, which is supplied the whole treatment, and heat applied untll the iron is reduced to the metall cgstate and a titanium nitrogencompound 1 is formed. Temperatures from 1200 to 140.09. C. have given good results.

The application of heat is continued unt1l f coarse sand.

. This powder is subjected to lixiviation I I with dilute acid,

preferably sulfuric acid,- and the lixiviation 1s convenientlycarried out according to the. counter current principle.

The acid willdissolve out the iron but not the titaninum nitrogen compound, and care is taken that sufiicient acid isused to dissolve I a5 all iron presents-i In this example Iwill for' convenience only-refer 'to sulfuric acid although it is understood thatjother'acidsfsuch as hydrochlor c and nitric can beused;

From-the :lixiviation' there results a solu tion containing ferrous sulfate and a resi-' flue-consisting? principally of titanium nltrogencompounds together with silica and other impurities originally contained in the ilmenite. After being Chilled.thlS' IfSlduQfllS a suitable condition for further-{treatment to recover therefrom the titanium and the ni- Q trogen in the form of useful products. It is.

known from literature that titanium-cya nonitrids on heatin in the presence of steam form NH,,, Hdll and H, the titanlum being transformed to T iO I can make use of these reactions in my process'if it isdesired to produce HCN, but in thisspecific illustration of process I will produce ammonium sulfate from the nitrogen fixed by very simple operation.-

' I mix th dri d residue thoroughly with concentrated sulfuric acid in ap roximately the proportion two parts by welghtof 90% sulfuric acid to one part by weight of residue The mixture is now heated by means-of titanium, as this can be accomplished by a V and. place the mixture in a cast-iron'vessel.

steam or hot air until reaction-takesplace.

The heating is then discontinued and the re-" action proceeds throughout the whole mass.

color, consisting principallyof titanium sulfate and ammonium sulfate with small amounts of ferrous sulfate. I have found that when "proceeding as cally no nitrogen is lost.

The reaction product 1s a solid mass, of grey The mass thus obtained be subjected described practiw to various treatments for the manufacture of pure titanium compounds and ammonium sulfate.

of the resultant mass with-water or dilute acid, whereby the rrous sulfate present will dissolve, practi lly pure TiO,, will remain, as a residue.

lixiviate the mass obtained by thetreatment cording to the counter current principle.

I then use about four partsby weight '01 water to one part by'w'eight of solid mass. Thereresults a concentrated solution .of titanium sulfate; ammonium -sulfate and small amounts of ferrous sulfate. The resioriginal ore,is.,then removedfrom the solution.

titanium is precipitated in the orm 0f a I canheat the mass to above 400 C. whereby the sulfates of ammonia and titanium are decomposed. After lixiviation I prefer, however, to

with sulfuric acid directly with water ac I due consisting principally ofsilicajffromthe The-solution is heated to boilin whereby hydrate containing asmall' amount of'sul- 7 -furic acid. Thisfis j separated fromthe solution by means offiltering, washed, and

fer, however, to produce a pigment from this product and to this end I treat it according undesired acid substance containing theSO, radical. which comes-down on precipitation is then in itself a valuable product. a I pre, "120 'to Norwegian Patent No. 27,604 with barium chloridlorfsimilar compounds whereby the" .iisneutralized. On calcination according to'if fNorwegian I at ent-l T 28,216 I obtain a productcons stmg principally; of titanium-1 oxid:partly-'orwholly in the crystallineform gandfalsocontaining about 20% of. barium sulfate. Asset forth in the said Norwegian patent a productconsisting principally of iO in the crystalline form and with the structure therein described is very well adapted for use as a pigment." This pig-- ment, however, I do not claim as my invention but only my method of producmg-it.

. The solution from which the titanium hydrate has been precipitated contains ammonium sulfate, small amounts of iron sulfate and free sulfuric acid liberated by the precipitation of titanium hydrate. The. am-

.monium maybe recovered therefrom bymeans of distillation after an excessof'a base such as Ca(OH). has been 'addedto' the solution. But as'the" solution contains a considerable amount of acid: I prefer to evaporate the solution until ammonium sulfate crystallizesout. This is separated from the solution and is then in a form'suitablefor'use as a fe'rtilizen. The iron contained therein will dono harm if the product is used as a fertilizer. If an absolutely'pure ammonium sulfate is desired the product above described may be refined accordingto known methods, such as a repeated crystallization. The sulfuric acid which remains after the crystallization of ammonium sulfate I use for the lixiviation of iron as described in the first part of my process. i s

. What I claim as new and desire to secure by Letters Patent of the United States is:

1. The process ofpreparing titanium compounds from titaniferous material containing iron, which comprises heating a titaniferous material containing iron together with a reducingagent in an atmosphere of nitrogen until .a titanium nitrogen compound is formed and the iron present is reduced to the metallic state, dissolving said metallic iron in acid, and separating the solution y "from the residue containing the titanium nitrogen compound.

7 2. The process of preparing titanium compounds from titaniferousumateria'l containing'iron, which comprisesheating a.titaniferous materialcontaining iron together withcarbon in an atmosphere of nitrogen until a titanium nitrogen compound 1s formed and the iron'present is reduced to the metallic state, dissolving said metallic ironin acid,--

and separating the solution from the residue containing the titanium nitrogen compound.

compounds from titaniferous material conv 3; The process of preparing titanium taining iron, which comprises heating a titaniferous materialcontainingiron together -with carbon-in an atmosphere ofynitrogen until a titanium-nitrogen compound and also another titanium-nitrogen compound contamlng carbon are formed and the ron present is reduced to the metallic. state, dissolving said metallic iron in acid, and separating the solutlon from the residue con- Jsulfate andammonium sulfate, and separat- .taining iron, which comprises heating a 3 titanium sulfate and ammonium'sulfate, dis- "p'recipitate from the( solution.

taining the titanium nitrogen compound and also the titanium nitrogen compound containing carbon. I

. 4. The process. ofpreparing titanium compounds from titaniferous materials con-. taining iron, which comprises heating a titaniferous material containing iron together I with carbon in an atmosphereof. nitrogen until a titanium nitrogen compound is formed and the iron present is reduced'to the metallic state, dissolving said metallic viron in acid and separating the solution from the residue containing the titanium nitrogen compound,'heating'said residue together with sulfuric acid to form-titanium ing these sulfates.

5. The process of preparing titanium compounds from titaniferous materials contitaniferous material containing iron together with carbon in an atmosphere of nitrogenuntil a titanium nitrogen oo'm pound is formed and the'iron. present is reduced to the metallic 'fstate, dissolving 9' said metallic iron in acid-land separating "the solution from the residue containing the titanium nitrogen compound, heating said residue together with sulfuric acid to form solving said sulfates in water, heating the solution thus formed until'a titanium hy-' drateis precipitated, and separating 'the 6. The process o f compounds from .titaniferous material" 0011.1 taining iron, which comprises heating a titaniferous' material: containing iron to-.' gether with carbpn inan atmosphere of nitrogen until a titanium 'nitrogen. com: 10-5. pound is formed and the iron present is reduced tothe metallic state, dissolving said metallic 'iron in acid and separating the solution from the residue containing the titanium nitrogen compound, heating said residue together with sulfuric acid to form titanium sulfate and ammonium sulfate,

dissolving said sulfates in water, heating the solution thus formed until a titanium Y hydrate isprecipitated, separatingthe precipitate from the-solution, and crystallizing out the ammonium sulfate from the solu-' tion. I

7. The process of preparing titanium compounds fromtitaniferous material co ntaining iron, which comprises heating a titaniferous material containing iron to preparingtitanium I 1001 v sulfate and ammonium sulfate, dissolving said sulfate in water, heating the solution thus formed until a titanium h drate containing a small amount of the the precipitate form barium sulfate with the SO radical present. 10

8. The process 'of preparing titanium compounds from-titaniferous materials containin titani erous material containing iron together with carbon in an atmosphere of ni--- trogen until a-titan'ium nitrogen compound isformed and theiron present is reduced to the metallic state, dissolving said metallic iron, in acid separating the solution.

from residue containing the titanium nitrogen compound, heating said residue togther with sulfuric acid to form titanium sulfate'aiad ammonium' sulfate, dissolving said sulfates in water, heating the solution thus formed until a titaniumhydrate cona small amount of SO radical is tai'ning precip tated, separating the precipitate from the solution, washing the precipitate and v treating it with a barium compound to form.

5 barium sulfate with-the SO, radical present,

' Ti O and barium sulfate."-

and calciningthe resulting product to form 9. The process of. preparing titanium I compounds from titaniferous material containing iron, "which-comprises heating a titaniferous J materialjcontaining, iron to- & 'gether with carbon in' an atmosphere of nitrogen juntil a"titaniumnitrogen comis formed and the iron present is the solution from the residue containing jthe titanium-nitrogen compound, heating reduced to the metallic state, dissolving said metallic iron in acid and separating saidresidue together. with sulfuric acid to form titanium sulfate and ammoniumsulfate, dissolving said sulfates in water,, 'heating the solution thus; formed/until" a titanium hydrate amount of SO radical is-precipitated, sepcontaining a small ,arating' the precipitate from the "solution, washing the'precipitate and treating it with a, barlum com ound .to form barium sul O; radical present, and calcining the resulting product to' form crys-' fate with the talline TiO 10. The processfof preparing titanium compounds from 'titaniferous materials containing iron, which comprises heating a titan'iferous material containing iron' together' with carbon in an atmosphere of nitrogen until a titanium nitrogen compound is formed and the iron present is re- O radical is precipitated, separating the precipitate from the solution, washing and treating it with a barium compound to iron, which comprises heating .a.

state n t the mania state, dissolvin said metallic iron in dilute sulfuric, aci and separating the solution'from theresidue containmg "the titanium nitrogen compound, he'ating said residue together" with sulfuric acid to form titanium sulfate and ammonium sulfate, dissolving said sulfates in water, heating the solution thus formed until a titanium hydrate containing a small amount of. SO radical is precipitated,

separating the precipitate from the solution, washing the precipitate and treating it with a barium compound to form barium sulfate-with the S0 radical present, and calcining the resulting. product to form crystalline TiO 11. In the recovery of titanium from titaniferous material, the process -which' I comprisesthe step of heating the titaniferous material in the presence of nitrogen,

and a reducing agent, at'such temperatures andfor such a time that decomposition o'f' the titaniferous material is efi'ected and a titanium nitrogen compound formed.

12. In the recovery of titanium from titaniferous material containing iron, the 1 process which comprises the step of heating 7 the titaniferous material in the presence of nitrogen and a reducing agent, at such temperatures and for such a time that decomfected, and a titanium nitrogen compound formed and the iron reduced to a metallic the .recov er'yof titanium and.

.poSition of the titaniferous jmaterial is eftitaniferous materials containing iron, th'e process which comprises the step of heating the 'titaniferous material. with carbon in the presence of. nitrogen, at such tema perature and for such a time that decomposition of the titaniferous material is ef-' fectedand a titanium nitrogen compound j formed and the iron'reduced to a metallic v tanium nitrogen compound is formed and the iron reduced to a metallic state, re-

moving the iron from the decomposition product, subjecting the remainder of the said product -to further treatment whereby a'titaniumoxygen. compound is formed,

and recoverin Signed at. 5th day of February, 1918.

PEDER' FARUP'.

the said compound;

hristiania","- Norway, on" this 

